EP0777703B1 - Dicyclic metal complex formazan derivatives, process for producing the same, composition containing the same and dyeing process employing the same - Google Patents

Dicyclic metal complex formazan derivatives, process for producing the same, composition containing the same and dyeing process employing the same Download PDF

Info

Publication number
EP0777703B1
EP0777703B1 EP96909386A EP96909386A EP0777703B1 EP 0777703 B1 EP0777703 B1 EP 0777703B1 EP 96909386 A EP96909386 A EP 96909386A EP 96909386 A EP96909386 A EP 96909386A EP 0777703 B1 EP0777703 B1 EP 0777703B1
Authority
EP
European Patent Office
Prior art keywords
formula
compound
dicyclic
group
formazan
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP96909386A
Other languages
German (de)
French (fr)
Other versions
EP0777703A2 (en
Inventor
Dong Gil Kim
Sung Yong Cho
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kyungin Synthetic Corp
Original Assignee
Kyungin Synthetic Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kyungin Synthetic Corp filed Critical Kyungin Synthetic Corp
Publication of EP0777703A2 publication Critical patent/EP0777703A2/en
Application granted granted Critical
Publication of EP0777703B1 publication Critical patent/EP0777703B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/4401—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system
    • C09B62/4403—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system the heterocyclic system being a triazine ring
    • C09B62/4407—Formazane dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B50/00—Formazane dyes; Tetrazolium dyes

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Coloring (AREA)
  • Plural Heterocyclic Compounds (AREA)

Description

    Technical Field
  • The present invention relates to formazan derivatives useful as reactive dye and a process for producing the derivatives. More specifically, the present invention relates to a novel dicyclic metal complex formazan derivatives used as a light blue dye and a process for producing the derivatives.
    • Background Art
  • Generally, metal complex formazan derivatives are used as complex salt of divalent or trivalent metal such as copper, nickel, cobalt and chromee, have brighter colors than conventional azo dyes, and have an excellent compatibility with the other color dyes as compared with anthraquinone or dioxazine- based dyes.
  • Formazan derivatives as reacive dyes which have a form of copper complex or have a vinylsulfone group or both of vinylsulfone group and monochlorotriazine, have been developed long time ago. The conventional formazan are mostly tricyclic. Most of them are 2-carboxyl-5-sulfo-phenylhydrazine as hydrazine compound. These tricyclic formazans are expensive in manufactruing and poor in stability for alkali at the time of room tepperature immersion (cold pad) dyeing.
  • Typical tricyclic formazan compounds have the following formula:
    Figure 00020001
    Specifically, Japanese Patent Publication No.81-4783 describes a compound represented by the below formula:
    Figure 00020002
  • However, the said compound of Japanese Patent Publication No.81-4783 is not good in solubility, dyeing property and state of remained bath. In addition, Japanese Patent Publication Sho 55-12187 and EP 0,099,721 disclose tricyclic formazan derivatives as dye similiar to the compound of the Japanese Patent Publication No.81-4783. But, these dyes are expensive in manufacturing cost and are not good in fastness.
  • Further, United Kingdom Patent Publication 1,194,504 discloses dicyclic formazan derivatives having the following formula:
    Figure 00030001
  • The said dicyclic formazan derivatives is also not good in fastness and dyeing property.
  • USP 4,607,098 discloses a compound of the following formula which has more improved fastness than the said dicyclic formazan derivatives:
    Figure 00040001
    However, these formazan compounds known in USP 4,607,098 have also somewhat problems in dyeing property and chlorine water.
    • Disclosure of the Invention
  • The inventors have made extensive and intensive sutdies with a view to solving the above-described problems, and thereby have obtained novel formazan derivatives represented by the below formula(1):
    Figure 00040002
    wherein
  • A is benzene or naphthalene having 1 to 3 substituent groups and sulfo group(-SO3M) in ortho-position for N-atom of hydrazone compound;
  • B is strait- or branched-chain alkyl group, phenyl group, naphthyl group or substituent heterocyclic group;
  • C is benzene or naphthalene having from 1 to 3 substituent groups;
  • D is benzene or naphthalene;
  • M is hydrogen atom, alkali metal or alkaki earth metal;
  • Me is metal ion of atomic number 27 to 29;
  • Y is halogen;
  • X is halogen atom or sulfo group, carboxyl group, phosphonic group providing solubility for water;
  • R is strait- or branched-chain alkyl group;
  • Q is -SO2CH=CH2, or -SO2CH2CH2L(L is a group which may be substituted by alkali); and
  • l,m,n are independently an intenger from 0 to 3.
  • Formazan derivatives represented by the above formula(1) are produced by firstly condensing formazan compound of the below formula(2) with 1,3,5-trihalogeno-s-triazine to give formazan compound of the below formula(3), and secondly condensing the obtained formazan compound of the formula(3) with amine compound of the below formula(4):
    Figure 00060001
    Figure 00060002
    Figure 00060003
  • Alternatively, formazan derivatives of the formula(1) are produced by reacting 1,3,5-trihalogeno-s-triazine with the amine compound of the formula(4) to give a compound of the below formula(5), and then reacting the obtained compound of the formula(5) with formazan derivatives of the formula(2):
    Figure 00070001
  • The definitions in the compounds of the above formula(2) and (3) are same as in the compound of the formula(1). However, the substituents of benzene or naphthalene ring in definitions A and C are preparably halogen, nitro, C1-C4 alkyl group, C1-C4 alkoxy group, sulfamoyl group, N-mono or N,N-dialkyl(C1-C4)sulfamoyl, C1-C4 alkylsulfonyl group, phenylsulfonyl group, more preferably chlorine, bromine, nitro, methyl, ethyl, methoxy, ethoxy, sulfamoyl or N,N-dimethylsulfamoyl group.
  • If B is a strait or branched chain, it is preferably C1-C8, more preferably C2-C8.
  • If B is a benzene or naphthalene, the substituent is preferably halogen, hydroxy group, nitro group, C1-C4 alkyl, C1-C4 alkoxy group, C1-C4 carboalkoxy group.
  • If B is heterocyclic ring, the substituent is preferably furan, thiophen, pyrrol, imidazole, indol, pyrazole, pyridine, pyrimidine, quinoline, benzimidazole and the like. Hydrogen atom bonded to the ring-membered carbon consisting of heterocyclic ring may be substituted with chloro, phenyl, methyl, ethyl, methoxy or ethoxy, and hydrogen atom bonded to hetero atom of the heterocyclic ring may be substituted with methyl, ethyl or benzyl.
  • Me as metalic atom is preferably a compound of atomic number 27 to 29, more preferably atomic number 29, Cu.
  • In the compounds of the above formula(1),(3) and (5), halogen of definition Y is preferably fluorine, chlorine or bromine atom, more preferably fluorine or chlorine atom.
  • X group providing solubility for water, is preferably sulfonic acid, carboxylic acid or phosphonic acid, more preferably sulfonic acid, which may be bonded to ring-membered carbon atom consisting of ring or to aliphatic carbon atom linked to ring.
  • In the compounds of the above formula(1), (4) and (5), if D is phenyl, it may be substituted with halogen, C1-C4 alkyl group or C1-C4 alkoxy group, preferably methyl, ethyl, methoxy, ethoxy, chlorine or bromine. And if D is naphthalene, it is preferably unsubstituted or substituted with sulfonic group.
  • Further, in the compounds of the formula(1),(4) and (5), if R is alkyl group, it is preferably low alkyl groups such as methyl, ethyl, propyl and butyl, more preferably methyl, ethyl, carbamoyl, ethyl, hydroxyethyl, n-propyl, isopropyl and the like, which may be substituted with hydroxyl, carboxyl, sulfo, carbamoyl, methoxy carbonyl group and the like.
  • l,m and n indenpendently, are preferably 2 or 3.
  • In the compounds of the above formula(1),(4) and (5), if Q is -SO2CH2CH2L, L is preferably ester group, -OPO3H2, -SSO3H2, more preferably -OSO3H of organic carboxylic acid or sulfonic acid comprising chlorine, bromine atom or acetyloxy group, benzoyloxy group, benzene sulfonyloxy group and low alkane oxy group.
  • Accordingly, Q can be represented by -SO2CH2CH2OSO3H, wherein a part of these elements may be removed by alkali to give a form of -SO2CH=CH2.
  • A group of the below formula(5') in the formula(1) may be linked to any one of phenyl, naphthyl, alkyl, alkenyl, phenylene, naphthalene, heterocycle or carbon atom of branched-chain, preferably phenyl group:
    Figure 00100001
  • Formazan derivatives of the formula(1) according to the above preferable definitions are represented by the below formula(6):
    Figure 00100002
    5 wherein D,R,Q and Y are same as defined in the formula(1),(3),(4) and (5), p,q and r are indenpendently 0 or 1, provided that the total amount of them is an intenger of 3 or less.
  • More preferable formazan derivatives is represented by the below formula(6'):
    Figure 00110001
  • Most preferable formazan derivatives is represented by the below formula(6");
    Figure 00110002
  • Formazan derivatives of the formula(1) according to the present invention are produced by reacting a formazan compound of the above formula(2) with 1,3,5-trihalogeno-s-triazine to give a formazan compound of the below formula(3), and condensing the obtained formazan compound of the formula(3) with an amine compound of the above formula(4); or by reacting 1,3,5-trihalogeno-s-triazine with the amine compound of the formula(4) to give a compound of the below formula(5), and then reacting the obtained compound of the formula(5) with formazan derivatives of the formula(2) .
  • Reaction conditions and order in this process are not specifically limited, the condensation reaction are conducted generally at pH 2 to 8 and temperature of -5 to 70°C, preferably pH 3 to 6 and temperature of 0 to 60°C.
  • More specifically, the reaction condition in the first condensation may depend on physical properties of the reactants or intermediates to be produced, but is relatively low pH and reaction temperature. That is to say, the first condensation reaction is conducted at pH 2 to 4 and temperature of -5 to 20°C, preferably pH 3 to 4 and temperature of 0 to 10°C.
  • But, the second dondensation reaction depends on physical prorerties of reactants and formazan derivatives to be produced, and is conducted at relatively high pH, for example pH 4 to 8 and relatively high temperature of 20 to 70°C, preferably pH 4 to 6 and relatively high temperature of 30 to 60°C.
  • Formazan derivatives of the formual(2) can be produced by diazotating an amine compound of the below formula(7) to give a sulfone compound, hydrolizing the obtained sulfone compound in the presence of inorganic acid to give hydrazine compound, reacting the obtained compound with aldehyde compound of the formula(8) to synthesize hydrazone compound, reacting the obtained hydrazone compound with the compound of the below formula(9) to diazotate it, and then coupling them in the presence of metal ion:
    Figure 00130001
    Figure 00130002
    Figure 00130003
  • If the above obtained compound is not amine compound of the formula(2) but compound of the below formula(10) having nitro or acetylamino group, the compound of the formula(2) can be easily produced by reduction of nitro group or hydrolysis of acetylamino group:
    Figure 00140001
    wherein T is nitro group or acetylamino group, and definition for the other symbols are same as these of the above formula(1).
  • Metal ion used in this process are sulfate, carbonate, acetate, salisilate, tartarate or chloride which concerns in the reaction.
  • Examples of the compound represented by the forumla(7) are aniline-2-sulfonic acid, aniline-2,4-disulfonic acid, aniline-2,5-disulfonic acid, 4-methylaniline-2-sulfonic acid, 5-methylaniline -2-sulfonic acid, 2,4-dimethylaniline-2-sulfonic acid, 4,5-dimethylaniline-2-sulfonic acid, 2-methylaniline-4,6-disulfonic acid, 4-methylaniline-2,5-disulfonic acid, 4-methoxyaniline-2-sulfonic acid, 5-methoxyaniline-2-sulfonic acid, 4-methoxy-5-chloroaniline-2-sulfonic acid, 4,5-dimethoxyaniline-2-sulfonic acid, 4-ethoxyaniline-2-sulfonic acid, 5-ethoxyaniline-2-sulfonic acid, 4-hydroxyaniline-2-sulfonic acid, 5-hydroxyaniline-2-sulfonic acid, 5-hydroxyaniline-2,4-disulfonic acid, 4-carboxylaniline-2-sulfonic acid, 5-carboxylaniline-2-sulfonic acid, 4-hydroxy-3-carboxylaniline -2-sulfonic acid, 4-nitroaniline-2-sulfonic acid, 5-nitroaniline-2-sulfonic acid, 2,4-dinitroaniline-6-sulfonic acid, 5-nitro-4-chloroaniline-2-sulfonic acid, 4-fluoroaniline-2-sulfonic acid, 3-chloroaniline-2-sulfonic acid, 4-chloroaniline-2-sulfonic acid, 5-chloroaniline-2-sulfonic acid, 4,5-dichloroaniline-2-sulfonic acid, 2,4-dichloroaniline-6-sulfonic acid, 2,4,5-trichloroaniline-2-sulfonic acid, 4-chloro-5-carboxylaniline-2-sulfonic acid, 2,5-dichloro-4-nitroaniline-6-sulfonic acid, 4-bromoaniline-2-sulfonic acid, 5-bromoaniline-2-sulfonic acid, 2,4-dibromoaniline-6-sulfonic acid, 3,4-dibromoaniline-6-sulfonic acid, 4-iodoaniline-2-sulfonic acid, 5-iodoaniline-2-sulfonic acid, 4-acetaminoaniline-2-sulfonic acid, 5-acetaminoaniline-2-sulfonic acid, 1,4-phenylenediamine-2,5-disulfonic acid, 1,3-phenylenediamine-4,6-disulfonic acid, 1-naphthylamine-2-sulfonic acid, 2-naphthylamine-1-sulfonic acid, 1-naphthylamine-2,4-disulfonic acid, 1-naphthylamine-2,5-disulfonic acid, 2-naphthylamine-1,5-disulfonic acid, 2-naphthylamine-1,7-disulfonic acid, 2-naphthylamine-3,6-disulfonic acid, 2-naphthylamine-3,7-disulfonic acid, 1-naphthylamine-2,4,7-trisulfonic acid, 2-naphthylamine-3,6,8-trisulfonic acid, 2-naphthylamine-1,5,7-trisulfonic acid.
  • Examples of the aldehyde compound represented by the forumla(8) are benzaldehyde, 2-methoxybenzaldehyde, 3-methoxy benzaldehyde, 4-methoxybenzaldehyde, 4-methoxybenzaldehyde-3-sulfonic acid, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methoxy-3-chlorobenzaldehyde, 2-nitrobenzaldehyde, 3-nitrobenz aldehyde, 2-hydroxybenzaldehyde, 2-chlorobenzaldehyde, 4-chlorobenzaldehyde, 2,4-dichlorobenzaldehyde, 2-chlorobenzaldehyde -5-sulfonic acid, benzaldehyde-2-sulfonic acid, benzaldehyde-3-sulfonic acid, benzaldehyde-4-sulfonic acid, benzaldehyde-2,4-disulfonic acid, 2-acetylaminobenzaldehyde, 4-acetylaminobenz aldehyde, 4-nitrobenzaldehyde-2-sulfonic acid, 3-methyl-2-nitrobenzaldehyde, 3-methyl-6-nitrobenzaldehyde, 2-chloro-6-nitrobenzaldehyde, 1-naphthoaldehyde, 2-naphthoaldehyde, furan-2-aldehyde, thiophene-2-aldehyde, pyrrol-2-aldehyde imidazole-2-aldehyde, pyrazole-5-aldehyde, pyridine-2-aldehyde, pyridine-3-aldehyde, pyridine-4-aldehyde, pyrimidine-5-aldehyde, quinoline-4-aldehyde, benzimidazole-2-aldehyde, acetaldehyde, buthylaldehyde, ethanealdehyde, acrylaldehyde, crotonaldehyde, phenacetaldehyde, cinamaldehyde.
  • Examples of the amine compound represented by the forumla(9) are 2-aminophenol, 4-methyl-2-aminophenol, 5-methyl-2 - aminophenol, 4-sulfo-2-aminophenol, 5-sulfo-2-aminophenol, 4-methoxy-2-aminophenol, 5-methylsulfonyl-2-aminophenol, 4-methyl sulfamoyl-2-aminophenol, 4-dimethylsulfamoyl-2-aminophenol, 5-nitro-2-aminophenol, 4-bromo-2-aminophenol, 4,6-disulfo-2-aminophenol, 2-acetylamino-6-aminophenol-4-sulfonic acid, 6-nitro-4-sulfo-2-aminophenol, 4-nitro-6-sulfo-2-aminophenol, 4-acetylamino-6-sulfo-2-aminophenol,
    4-chloro-6-sulfo-2-aminophenol, 6-chloro-4-sulfo-2-aminophenol, 4-methylsulfonyl-2-aminophenol, 4-buthylsulfonyl-2-aminophenol, 4-ethylsulfonyl-2-aminophenol, 4-sulfamoyl-2-aminophenol, 1-amino-2-hydroxynaphthalene-4,6-disulfonic acid, 1-amino-2-hydroxynaphthalene-6-chloronaphthalene-4-sulfonic acid, 4-methylol-6-sulfo-2-aminophenol.
  • Aromatic amine represented by the above formula(4) can be produced by alkylating aromatic amine of the below formula(11) in the presence of alkylating agent such as alkylhalide, dialkylsulfate, monosubstituted ethylene oxide: H2N-D-Q
  • Examples of alkylhalide are halides such as methylchloride, ethylchloride, n-propylchloride, isopropylchloride, n-buthylchloride, isobuthylchloride, sec-buthylchloride, methylbromide, ethylbromide, n-propylbromide, isopropylbromide, n-buthylbromide, isobuthyl bromide, and sec-buthylbromide; and examples of mono substituted ethylene are acrylonitrile, acrylic acid, methylacrylate, ethylacrylate, acrylamide, and binylsulfonic acid.
  • Examples of dialkylsulfate are dimethylsulfate, diethylsulfate and dipropylsulfate; and examples of oxide are ethyleneoxide, propyleneoxide, glycol, trimethyleneoxide, β-buthyloxide, 2-methyl-α-buthyleneoxide, 2-ethyl-3-methyleneoxide, methoxyethyleneoxide, methoxyleneoxide and n-buthoxyyleneoxide.
  • Aromatic amine compound of the above formula(11) can be produced by esterizing or halogenizing a compound of the below formula(12): H2N-D-SO2CH2CH2OH
  • Examples of aromatic amine compound represented by the above formula(11) which cna be produced by the said process, are 1-aminobenzene-2,3-β-sulfatoethylsulfone, 1-aminobenzene-2,4-β-sulfatoethylsulfone, 1-aminobenzene-3-phosphatoethylbenzene, 1-amino-4-methylbenzene-3-β-sulfatoethylsulfone, 1-aminobenzene-3-β-phosphatoethylbenzens, 1-aminobenzene-4-methoxybenzens-3-β-sulfatoethylsulfone, 1-amino-2,5-dimethylbenzene-4-β-sulfatoethylsulfone, 1-amino-4-methoxybenzene-4-β-sulfatoethylsulfone, 1-amino-4-chlorobenzene-4-β-sulfatoethylsulfone, 1-amino-4-methoxybenzene-5-β-sulfatoethylsulfone, 2-aminonaphthalene-8-β-sulfatoethylsulfone-6-sulfonic acid, 2-aminonaphthalene-8-β-sulfatoethylsulfone, 1-amino-2,5-dimethoxybenzene-4-vinylsulfone, 1-amino-2-methoxy-5-methylbenzene-4-β-sulfatoethylsulfone, 2-aminonaphthalene-4,5,6-β-sulfatoethylsulfone, 2-aminonaphthalene-4,5,7-β-sulfatoethylsulfone, 1-amino-2-bromobenzene-4-vinylsulfone, 2-amino-8-sulfonaphthalene-6-β-sulfatoethylsulfone, 2-aminonaphthalene-8-β-phosphatoethylsulfone-6-sulfonic acid, 2-aminonaphthalene-8-vinylsulfone-6-sulfonic acid, 1-amino-2-methoxy-5-methylbenzene-4-β-chloroethylsulfone, 1-aminobenzene-2,3-vinylsulfone, 1-aminobenzene-2,4-vinylsulfone, 1-amino-2-methoxy-5-chlorobenzene-4-β-chloroethylsulfone, 1-amino-2-methoxy-5-chlorobenzene-4-vinylsulfone, 1-amino-2-ethoxy-5-chlorobenzene-4-β-chloroethylsulfone, 1-amino-2-ethoxy-5-chlorobenzene-4-vinylsulfone, 2-aminonaphthalene-8-β-sulfatoethylsulfone-1-sulfonic acid, 5-chloroaniline-2-β-sulfatoethylsulfone, 5-sulfoaniline-2-β-sulfatoethylsulfone, aniline-2-β-thiosulfatoethylsulfone, 5-chloroaniline-2-β-thiosulfato ethylsulfone, 5-sulfoaniline-2-β-thiosulfatoethylsulfone, aniline-2-β -phosphatoethylsulfone, 5-chloroaniline-2-β-phosphatoethylsulfone, 5-sulfoaniline-2-β-phosphatoethylsulfone, 5-chloroaniline-2-vinylsulfone, 5-sulfoaniline-2-vinylsulfone, aniline-2-β-chloro ethylsulfone, 5-chloroaniline-2-β-chloroethylsulfone and 5-sulfoaniline-2-β-chloroethylsulfone.
    • Best Mode for Conducting the Invention
  • Process for preparing formazan derivatives according to the present invention is more specifically described in the following examples, however the present invention is not intended to be restricted to the examples.
    • Example 1
  • Phenylhydrazine-2,5-disulfonic acid is produced by diazotating aniline-2,5-disulfonic acid of the formula(7). 35.6 parts of benzaldehyde phenylhydrazone-2,5-sulfonic acid is produced by reacting the above obtained phenylhydrazine-2,5-disulfonic acid with benzaldehyde of the formula(8). 35.6 parts of phenylhydrazone-2,5-sulfonic acid is dispersed in 200 parts of water, and acidity of the dispersion is controled to pH 4 with a solution of 10% sodium hydroxide. 24.6 parts of 3-acetylamino -2-hydroxyaniline-5-sulfonic acid of the formula(9) is diazotated and added to the said pH-controled solution with stirring. Aquous solution obtained by solubilize 26.2 parts of copper sulfate to water is added thereto. pH of the solution is controled in the range from 3 to 5 with 20% sodium carbonate aquous solution obtained by solubilizing sodium carbonate and reaction is conducted for one hour. The reaction is conducted at elevated temperature of 40 to 50°C for one hour to complete the reacition. The reaction solution is cooled to the room temperatrue, and 20% of sodium chloride based on the entire solution is added to this solution, and stirred for one hour. The precipitate is filtered out to give formazan derivatives. The formazan derivatives is added to a solution of sodium hydroxide, hydrolized by heating at temperatureof 90 °C for one hour to obtain the product. As a result, dicyclic formazan derivatives represented by the below formula is obtained by removing acetyl group from the product:
    Figure 00220001
    • Example 2
  • Formazan derivatives obtained in Example 1 is acidified to pH 3 to 4 with concentrated hydrochloric acid, and 16.6 parts of cyanuric chloride are added thereto with maintaining them at temperature of 5°C for one hour to give formazan derivatives represented by the below formula(3):
    Figure 00230001
    • Example 3
  • To a solution containing formazan derivatives obtained in Example 2 are added 27.8 parts of 1-N-ethylaminobenzene-3-β-sulfatoethylsulfone produced by reacting 1-aminobenzene-3-β-sulfatoethylsulfone with diethylsulfate. The mixture is heated to temperature of 40°C, and is maintained at pH 5 to 6 for 25 hours.
  • To the reaction-completed solution is added sodium chloride to give preciitate which is filtered out to obtain blue(603 nm) formazan derivatives of the below formula:
    Figure 00240001
    • Examples 4 to 44
  • The procedures described in Example 3 are repeated in a solution containing formazan derivatives obtained in Examples 1 and 2 by using the following compounds instead of compounds used in Examples 1 and 2. As a result, blue(603±2nm) formazan derivatives are obtained.
    Example No. Used compounds
    4 1-N-ethylaminobenzene-4-β-sulfatoethylsulfone
    5 1-N-ethylaminobenzene-2-β-sulfatoethylsulfone
    6 1-N-methylamino-4-methoxybenzene-3-β-sulfatoethylsulfone
    7 1-N-methylaminobenzene-3-β-sulfatoethylsulfone
    8 1-N-methylaminobenzene-4-β-sulfatoethylsulfone
    9 1-N-methylaminobenzene-2-β-sulfatoethylsulfone
    10 1-N-methylamino-4-methoxybenzene-3-β-sulfatoethylsulfone
    11 1-N-β-carbamoylethylaminobenzene-3-β-sulfatoethylsulfone
    12 1-N-β-carbamoylethylaminobenzene-4-β-sulfatoethylsulfone
    13 1-N-β-carbamoylethylaminobenzene-2-β-sulfatoethylsulfone
    14 1-N-β-carbamoylmethylamino-4-methoxybenzene-3-β-sulfatoethylsulfone
    15 1-N-n-propylaminobenzene-3-β-sulfatoethylsulfone
    16 1-N-n-propylaminobenzene-4-β-sulfatoethylsulfone
    17 1-N-n-propylaminobenzene-2-β-sulfatoethylsulfone
    18 1-N-n-propylamino-4-methoxybenzene-3-β-sulfatoethylsulfone
    19 1-N-β-cyanoethylaminobenzene-3-β-sulfatoethylsulfone
    20 1-N-β-cyanoethylammobenzene-4-β-sulfatoethylsulfone
    21 1-N-β-cyanoethylaminobenzene-2-β-sulfatoethylsulfone
    22 1-N-β-cyanoethylamino-4-methoxybenzene-3-β-sulfatoethylsulfone
    23 1-N-β-hydroxyethylaminobenzene-3- β-sulfatoethylsulfone
    24 1-N-β-hydroxyethylaminobenzene-4-β-sulfatoethylsulfone
    25 1-N-β-hydroxyethylaminobenzene-2-β-sulfatoethylsulfone
    26 1-N-β-hydroxyethylaminobenzene-4-methoxybenzene-3-β-sulfatoethylsulfone
    27 1-N-β-sulfatoethylaminobenzene-3-β-sulfatoethylsulfone
    28 1-N-β-methoxycarbonylethylaminobenzene-3-β-sulfatoethylsulfone
    29 1-N-ethylamino-2-methoxybenzene-5-β-sulfatoethylsulfone
    30 1-N-ethylamino-2,4-dimethylbenzene-5-β-sulfatoethylsulfone
    31 1-N-ethylamino-2-methoxy-5-methylbenzene-3- β-sulfatoethylsulfone
    32 1-N-ethylaminonaphthalene-6-β-sulfatoethylsulfone
    33 1-N-ethylamino-8-sulfonaphthalene-6- β-sulfatoethylsulfone
    34 1-N-methylaminonaphthalene-8-β-sulfatoethylsulfone
    35 1-aminobenzene-4-β-sulfatoethylsulfone
    36 1-aminobenzene-2-β-sulfatoethylsulfone
    37 1-aminobenzene-3-β-sulfatoethylsulfone
    38 1-amino-4-methoxybenzene-3-β-sulfatoethylsulfone
    39 1-amino-2-methoxybenzene-5-β-sulfatoethylsulfone
    40 1-amino-2-methoxy-5-methylbenzene-5-β-sulfatoethylsulfone
    41 1-amino-2,4-dimethylbenzen-5- β-sulfatoethylsulfone
    42 1-aminonaphthalene-6-β-sulfatoethylsulfone
    43 1-amino-8-sulfonaphthalene-6-β-sulfatoethylsulfone
    44 1-aminonaphthalene-8- β-sulfatoethylsulfone
    • Examples 45
  • The reaction is conducted at the same condition and procedure as those of Example 1, except that phenylhydrazine-2.4-disulfonic acid as a starting material is used instead of phenylhydrazine -2.5-disulfonic acid to give formazan derivatives represented by the below formula.
    Figure 00270001
    • Examples 46
  • The reaction between formazan derivatives produced from Example 45 and cyanurilchloride of Example 2 is conducted at the same reaction condition to give formazan derivatives represented by the below formula:
    Figure 00280001
    • Examples 47
  • Formazan derivatives produced in Example 46 is reacted with the same compounds and process as those of Example 3 to give a blue(606 nm) formazan derivatives:
    Figure 00280002
    • Examples 48 to 88
  • Formazan derivatives produced in Example 46 is reacted with the same compounds and process as those of Example 3, except that the following compounds are used instead of 1-N-ethylaminobenzene-3-β-sulfatoethylsulfone. As a result, blue(606± 2nm) formazan derivatives are obtained.
    Example No Used compounds
    48 1-N-ethylaminobenzene-4-β-sulfatoethylsulfone
    49 1-N-ethylaminobenzene-2-β-sulfatoethylsulfone
    50 1-N-ethylamino-4-methoxybenzene-3-β-sulfatoethylsulfone
    51 1-N-methylaminobenzene-3-β-sulfatoethylsulfone
    52 1-N-methylaminobenzene-4-β-sulfatoethylsulfone
    53 1-N-methylaminobenzene-2-β-sulfatoethylsulfone
    54 1-N-methylamino-4-methoxybenzene-3-β-sulfatoethylsulfone
    55 1-N-β-carbamoylethylaminobenzene-3-β-sulfatoethylsulfone
    56 1-N-β-carbamoylethylaminobenzene-4-β-sulfatoethylsulfone
    57 1-N-β-carbamoylethylaminobenzene-2-β-sulfatoethylsulfone
    58 1-N-β-carbamoylmethylamino-4-methoxybenzene-3-
    β-sulfatoethylsulfone
    59 1-N-n-propylaminobenzene-3-β-sulfatoethylsulfone
    60 1-N-n-propylaminobenzene-4-β-sulfatoethylsulfone
    61 1-N-n-propylaminobenzene-2-β-sulfatoethylsulfone
    62 1-N-n-propylamino-4-methoxybenzene-3-β-sulfatoethylsulfone
    63 1-N-β-cyanoethylaminobenzene-3-β-sulfatoethylsulfone
    64 1-N-β-cyanoethylaminobenzene-4-β-sulfatoethylsulfone
    65 1-N-β-cyanoethylaminobenzene-2-β-sulfatoethylsulfone
    66 1-N-β-cyanomethylamino-4-methoxybenzene-3-β-sulfatoethylsulfone
    67 1-N-β-hydroxyethylaminobenzene-3-β-sulfatoethylsulfone
    68 1-N-β-hydroxyethylaminobenzene-4-β-sulfatoethylsulfone
    69 1-N-β-hydroxyethylaminobenzene-2-β-sulfatoethylsulfone
    70 1-N-β-hydroxyethylaminobenzene-4-methoxybenzene-3-β-
    sulfatoethylsulfone
    71 1-N-β-sulfatoethylaminobenzene-3-β-sulfatoethylsulfone
    72 1-N-β-methoxycarbonylethylaminobenzene-3-β-sulfatoethylsulfone
    73 1-N-methylamino-2-methoxybenzene-5-β-sulfatoethylsulfone
    74 1-N-ethylamino-2,4-dimethylbenzene-5-β-sulfatoethylsulfone
    75 1-N-ethylamino-2-methoxy-5-methylbenzene-3-β-sulfatoethylsulfone
    76 1-N-ethylaminonaphthalene-6-β-sulfatoethylsulfone
    77 1-N-ethylamino-8-sulfonaphthalene-6-β-sulfatoethylsulfone
    78 1-N-methylaminonaphthalene-8-β-sulfatoethylsulfone
    79 1-aminobenzene-4-β-sulfatoethylsulfone
    80 1-aminobenzene-2-β-sulfatoethylsulfone
    81 1-aminobenzene-3-β-sulfatoethylsulfone
    82 1-amino-4-methoxybenzene-3-β-sulfatoethylsulfone
    83 1-amino-2-methoxybenzene-5-β-sulfatoethylsulfone
    84 1-amino-2-methoxy-5-methylbenzene-5-β-sulfatoethylsulfone
    85 1-amino-2,4-dimethylbenzene-5-β-sulfatoethylsulfone
    86 1-aminonaphthalene-6-β-sulfatoethylsulfone
    87 1-amino-8-sulfonaphthalene-6-β-sulfatoethylsulfone
    88 1-aminonaphthalene-8-β-sulfatoethylsulfone
  • Experiments for dyeing property for formazan derivatives of the present invention are conducted.
    • Experiment 1
  • 0.1 part of metal formazan derivatives having the below formula described in EP 0,099,721 and 0.1 part of metal formazan derivatives produced in Example 3 are separately melted in 200 parts of water to give a dyeing solution.
    Figure 00320001
    10 parts of sodium sulfate are added to the solution and then 10 parts of cotton cloth are added thereto. The solution is heated to temperature of 60°C. At this temperature, 4 parts of sodium hydrogen carbonate are added thereto and stirred for one hour.
  • Dyed cloth is washed by water, washed again by boiled soup water for 10 minutes, then washed by water to remove soup water, and dried. Dyeing property and remained concentration after washing soup water are compared and the results are shown in the below table.
    • Experiment 2
  • The procedure described in Experiment 1 is repeated, except that metal formazan compound of EP 0,099,721 and 0.2 part of metal formazan compound produced in Example 3 are solubilized in 200 parts of water to form a dyeing solution. Dyeing property and remained concentration after washing soup water are compared and the results are shown in the below table.
    • Experiment 3
  • The procedure described in Experiment 1 is repeated, except that metal formazan compound of EP 0,099,721 and 0.4 part of metal formazan compound produced in Example 3 are solubilized in 200 parts of water to form a dyeing solution. Dyeing property and remained concentration after washing soup water are compared and the results are shown in the below table.
  • Sunlight fastness and washing fastness for the dried cloth used in the experiments of the dyeing property are determined according to JIS L 0841 and JIS L 0844, and chlorine fastness in 20 ppm solution of sodium hypochloride is determined. The results are shown in Table.
    EP 0,099,721 The Present Invention
    Experiment 1 Dyeing Property 100 104.41
    Remained Concentration After Washing of Soup Water 100 76.64
    Experiment 2 Dyeing Property 100 105.63
    Remained Concentration After Washing of Soup Water 100 71.38
    Experiment 3 Dyeing Property 100 105.59
    Remained Concentration After Washing of Soup Water 100 73.35
    Sunlight Fastness 5 < 5-6
    Washing Fastness 4 5
    Chlorine Fastness 4 4
  • As seen from the above table, dicyclic metal formazan compound has excellent dyeing property as compared with the conventional tricyclic metal formazan compound. Further, the dye stuff withstand removing from fiber after washing the dyed cloth with soup water as well as has excellent post-dyeing sunlight and washing fastness.
  • Dicyclic metal formazan compound of the formula(1) can be also used as reactive dye in fiber having dydroxy group or amido group.

Claims (16)

  1. A dicyclic metal formazan derivative represented by formula(1) below:
    Figure 00350001
    A is benzene or naphthalene having 1 to 3 substituent groups and wherein sulfo group(-SO3M) is at the ortho-position in respect of the N-atom of hydrazone moiety;
    B is a straight- or branched-chain alkyl group, phenyl group, naphthyl group or substituent heterocyclic group;
    C is benzene or naphthalene having from 1 to 3 substituent groups;
    D is benzene or naphthalene;
    M is hydrogen atom, alkali metal or alkaki earth metal;
    Me is metal ion of atomic number 27 to 29;
    Y is halogen;
    X is halogen atom or sulfo group, carboxyl group or phosphonic group which provides solubility in water;
    R is a straight- or branched-chain alkyl group;
    Q is -SO2CH=CH2, or -SO2CH2CH2L (wherein L is a group which is capable of being substituted by alkali); and l,m,n are independently an integer from 0 to 3.
  2. A dicyclic metal formazan derivative according to Claim 1 represented by formula(6) below:
    Figure 00360001
  3. A dicyclic metal formazan derivative according to Claim 2 represented by formula(6') below:
    Figure 00360002
  4. A dicyclic metal formazan derivative according to Claim 3 represented by formula(6") below:
    Figure 00370001
  5. A dicyclic metal formazan derivative according to Claim 4 represented by the formula:
    Figure 00370002
  6. A dicyclic metal formazan derivative according to Claim 4 represented by the formula:
    Figure 00370003
  7. A dicyclic metal formazan derivative according to Claim 4 represented by the formula:
    Figure 00380001
  8. A dicyclic metal formazan derivative according to Claim 4 represented by the formula:
    Figure 00380002
  9. A process for producing a dicyclic formazan derivative of formula(1) below:
    Figure 00390001
    by firstly condensing a formazan compound of formula(2) below:
    Figure 00390002
    with 1,3,5-trihalogeno-s-triazine to give a formazan compound of formula(3) below:
    Figure 00390003
    and secondly condensing the obtained formazan compound of formula(3) with an amine compound of formula(4) below:
    Figure 00400001
  10. A process for producing a dicyclic formazan derivative wherein 1,3,5-trihalogeno-s-triazine is condensed with an amine compound of formula(4) below:
    Figure 00400002
    to give a compound of formula (5) below:
    Figure 00400003
    and then the obtained compound of formula(5) is condensed with a formazan derivative of formula(2) below:
    Figure 00400004
  11. A process for producing a dicyclic formazan derivative according to Claim 9 or 10, wherein the first condensation is conducted at pH 2 to 4 and temperature of -5 to 20°C, and the second condensation is conducted at pH 4 to 8 and temperature of 20 to 70°C.
  12. A process for producing a dicyclic formazan derivative according to Claim 11, wherein the first condensation is conducted at pH 3 to 4 and temperature of 0 to 10°C, and the second condensation is conducted at pH 4 to 6 and temperature of 30 to 60°C.
  13. A dicyclic metal formazan derivative represented by the below formula(2):
    Figure 00410001
       wherein
    A is benzene or naphthalene having 1 to 3 substituent groups and wherein sulfo group(-SO3M) is at the ortho-position in respect of the N-atom of hydrazone moiety;
    B is straight- or branched-chain alkyl group, phenyl group, naphthyl group or substituent heterocyclic group;
    C is benzene or naphthalene having from 1 to 3 substituent groups;
    M is hydrogen atom, alkali metal or alkaki earth metal;
    Me is metal ion of atomic number 27 to 29;
    X is halogen, or sulfo group, carboxyl group or phosphonic group which provides solubility in water; l,m,n are independently an intenger from 0 to 3, and wherein the dicyclic metal formazan derivative is not N-(2-hydroxy-3-aminophenyl-5-sulphonic acid)-N'-(phenyl-2',5'-disulphonic acid)-ms-phenylformazane.
  14. A process for producing a formazan derivative of formula(2) below:
    Figure 00420001
    wherein an amine compound of formula(7) below:
    Figure 00420002
    is diazotated to give a sulfone compound, the obtained sulfone compound is hydrolized in the presence of an inorganic acid to give a hydrazine compound, the obtained hydrazine compound is reacted with an aldehyde compound of formula(8) below: Xm―B―CHO to synthesize a hydrazone compound, the obtained hydrazone compound is reacted with the compound of formula(9) below:
    Figure 00430001
    to diazotate it, and then the obtained compound of formula(9) is coupled in the presence of metal ion.
  15. Use in a dye composition of a formazan derivative as defined in any one of Claims 1 to 8.
  16. A process for dyeing fabrics by using a dicyclic formazan derivative as defined in any one of claims 1 to 8.
EP96909386A 1995-04-08 1996-04-08 Dicyclic metal complex formazan derivatives, process for producing the same, composition containing the same and dyeing process employing the same Expired - Lifetime EP0777703B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
KR9508192 1995-04-08
KR1019950008192A KR0135648B1 (en) 1995-04-08 1995-04-08 Bicyclic metal complex formazen derivative thereof
PCT/KR1996/000049 WO1996033240A2 (en) 1995-04-08 1996-04-08 Dicyclic metal complex formazan derivatives, process for producing the same, composition containing the same and dyeing process employing the same

Publications (2)

Publication Number Publication Date
EP0777703A2 EP0777703A2 (en) 1997-06-11
EP0777703B1 true EP0777703B1 (en) 2003-06-25

Family

ID=19411789

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96909386A Expired - Lifetime EP0777703B1 (en) 1995-04-08 1996-04-08 Dicyclic metal complex formazan derivatives, process for producing the same, composition containing the same and dyeing process employing the same

Country Status (6)

Country Link
US (1) US5858026A (en)
EP (1) EP0777703B1 (en)
JP (1) JP2884190B2 (en)
KR (1) KR0135648B1 (en)
TR (1) TR199600978T1 (en)
WO (1) WO1996033240A2 (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT409144B (en) * 1996-06-21 2002-05-27 Chemiefaser Lenzing Ag METHOD FOR TREATING CELLULOSE FIBERS AND FORMS OF THESE FIBERS
US6632355B2 (en) * 2001-07-30 2003-10-14 Pentapure Incorporated Low spillage replaceable water filter assembly
US6407220B1 (en) * 2001-12-14 2002-06-18 Everlight Usa, Inc. Reactive formazan dyestuffs
KR100510236B1 (en) * 2002-06-11 2005-08-26 (주)경인양행 Blue Dye Mixture Of Metal Complex Formazan Derivatives
KR100531409B1 (en) * 2002-10-01 2005-11-28 (주)경인양행 Mixture dyes of metal complex formazan derivatives and methods for reactive dyeing with them
CN102295840B (en) * 2010-06-25 2013-12-11 上海雅运纺织化工股份有限公司 Navy blue reactive dye composition and dyeing application thereof to fibers
CN102311668B (en) * 2010-07-08 2013-09-18 上海雅运纺织化工股份有限公司 Blue reactive dye composition and dying application thereof on fiber
CN102311667B (en) * 2010-07-08 2013-12-04 上海雅运纺织化工股份有限公司 Navy reactive dye composition and dying application thereof on fiber

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH481998A (en) * 1967-02-17 1969-11-30 Geigy Ag J R Process for the production of reactive formazan dyes containing heavy metals
CH501714A (en) * 1968-01-29 1971-01-15 Ciba Geigy Ag Process for the production of fiber-reactive, heavy metal-containing formazan dyes
CH612448A5 (en) * 1974-12-20 1979-07-31 Ciba Geigy Ag
CH627206A5 (en) * 1978-07-06 1981-12-31 Ciba Geigy Ag
JPS6018357B2 (en) * 1979-06-20 1985-05-09 住友化学工業株式会社 Dyeing method for cellulose fibers
JPS5915451A (en) * 1982-07-19 1984-01-26 Sumitomo Chem Co Ltd Metal formazan compound, production thereof and method for dyeing fibrous material by using same
US4607098A (en) * 1984-07-19 1986-08-19 Hoechst Aktiengesellschaft Bicyclic copper complex formazan compounds having a fiber-reactive group of the vinyl sulfone series, containing a fiber-reactive group suitable as dyestuffs

Also Published As

Publication number Publication date
KR960037778A (en) 1996-11-19
KR0135648B1 (en) 1998-04-22
WO1996033240A3 (en) 1997-01-09
WO1996033240A2 (en) 1996-10-24
JP2884190B2 (en) 1999-04-19
US5858026A (en) 1999-01-12
JPH09510751A (en) 1997-10-28
TR199600978T1 (en) 1997-03-21
EP0777703A2 (en) 1997-06-11

Similar Documents

Publication Publication Date Title
EP0099721B1 (en) Reactive metal formazan blue dye
JPS6257665B2 (en)
EP0777703B1 (en) Dicyclic metal complex formazan derivatives, process for producing the same, composition containing the same and dyeing process employing the same
US5747657A (en) Reactive monoazo dyestuffs and the processes in which they are produced
JP2001510875A (en) Reactive dye containing piperazine
US5760215A (en) Fibre-reactive dyestuffs
JP2747500B2 (en) Fiber reactive phthalocyanine dye
US4128544A (en) Copper complexes of substituted sulfophenyl-azo-phenyl-azo-naphthalene sulfonic acids containing a heterocyclic fiber-reactive group
US4350632A (en) Water-soluble phthalocyanine compounds
US5847111A (en) Aluminum phthalocyanine reactive dyes
US6407220B1 (en) Reactive formazan dyestuffs
EP0611259B1 (en) Fibre-reactive phthalocyanine dyes
US4910298A (en) Monoazo compound having triazinyl bridging group and two vinylsulfone type fiber reactive groups imparting yellowish color
US5744622A (en) water-soluble, fiber-reactive anthraquinone compounds
JPS5958059A (en) Metal formazan compound, its preparation, and dyeing of fibrous material using it
JPH06212085A (en) Reactive dye and method of coloring fibrous material
JPH05202307A (en) Water-soluble azo compound, its production, and its use as dye
JPH06104778B2 (en) Metal formazan compound and method for dyeing or printing fiber material using the same
CS264149B2 (en) Process for preparing in water soluble trifendioxazines
KR910009919B1 (en) Process for the preparation of water-soluble copper complex disazo compounds
US20040059099A1 (en) Reactive azo dyes
JPS6040166A (en) Formazan copper complex compound, manufacture use of same asdyestuff
KR0159929B1 (en) Fibre-reactive dyestuffs
JPH0326766A (en) Manufacture of fiber-reactive formazan compound
KR20000050781A (en) A formazan dye compound including pyrimidine radical, and its preparing method

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19961217

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): BE

17Q First examination report despatched

Effective date: 19991228

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): BE

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20040326

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20090327

Year of fee payment: 14

BERE Be: lapsed

Owner name: *KYUNGIN SYNTHETIC CORP.

Effective date: 20100430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100430